Phosphoramidothionates

ABSTRACT

A compound of the formula: ##STR1## wherein R 1  is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lower cycloalkyl(lower)alkyl group, a halo(lower)alkyl group, a lower alkoxy(lower)alkyl group, a di(lower)alkoxy(lower)alkyl group, a cyano(lower)alkyl group, a lower alkylthio(lower)alkyl group, a lower alkynylthio(lower)alkyl group, a lower dioxothiacycloalkyl group, a lower thiacycloalkyl group, a lower oxacycloalkyl group, a lower oxacycloalkyl(lower)alkyl group or a thienyl(lower)alkyl group, R 2  is a lower alkyl group and R 3  is a 3,5-dimethoxyphenyl group, a 3,4-methylenedioxyphenyl group or a 4,5-methylenedixoy-2-nitrophenyl group, which is useful as a fungicide.

The present invention relates to phosphoramidothionates, and theirproduction and use.

The said phosphoramidothionates are representable by the formula:##STR2## wherein R₁ is a hydrogen atom, a lower alkyl group, a loweralkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lowercycloalkyl(lower)alkyl group, a halo(lower)alkyl group, a loweralkoxy(lower)alkyl group, a di(lower)alkoxy(lower)alkyl group, acyano(lower)alkyl group, a lower alkylthio(lower)alkyl group, a loweralkynylthio(lower)alkyl group, a lower dioxothiacycloalkyl group, alower thiacycloalkyl group, a lower oxacycloalkyl group, a loweroxacycloalkyl(lower)alkyl group or a thienyl(lower)alkyl group, R₂ is alower alkyl group and R₃ is a 3,5-dimethoxyphenyl group, a3,4-methylenedioxyphenyl group or a 4,5-methylenedioxy-2-nitrophenylgroup.

In the above significances, the term "lower" is intended to have notmore than 8 carbon atoms, and the term "halo" is intended to meanchlorine, bromine, fluorine and iodine, inclusively. Preferred R₁ is ahydrogen atom, a C₁ -C₅ alkyl group, a C₃ -C₄ alkenyl group, a C₃alkynyl group, a C₃ -C₆ cycloalkyl group, a C₃ cycloalkyl(C₂)alkylgroup, a halo(C₂ -C₃)alkyl group, a C₁ -C₂ alkoxy(C₂ -C₄)alkyl group, adi(C₁ -C₂)alkoxy(C₂ -C₃)alkyl group, a cyano(C₁ -C₃)alkyl group, a C₁alkylthio(C₃)alkyl group, a C₃ alkynylthio(C₂)alkyl group, a1,1-dioxotetrahydrothien-3-yl group, a tetrahydrothiopyran-4-yl group, atetrahydropyran-4-yl group, a tetrahydrofurfuryl group, atetrahydrofuryl group, a tetrahydrothienyl group or a 1-(thienyl)ethylgroup, and preferred R₂ is a C₁ -C₂ alkyl group.

The phosphoramidothionates (I) exhibit not only a preventive effect butalso a curative effect against plant diseases such as late blight anddowny mildew caused by infection of phytopathogenic fungi belonging toPhycomycetes. They also exhibit a systemic effect against abovementioned plant diseases. Thus, they are useful as fungicides.

Examples of phytopathogenic fungi belonging to Phycomycetes, againstwhich the phosphoramidothionates (I) can exert their fungicidalactivity, are as follows: Peronospora brassicae on vegetables andradish, Peronospora spinaciae on spinach, Peronospora tabacina ontobacco, Pseudoperonospora cubensis on cucumber, Plasmopara viticola ongrape, Plasmopara nivea on Umbelliferae plants, Phytophthora cactorum onapple, strawberry and carrot, Phytophthora capsici on tomato andcucumber, Phytophthora cinnamomi on pineapple, Phytophthora infestans onpotato, tomato and eggplant, Phytophthora nicotianae var. nicotianae ontobacco, kidney bean and onion, Pythium aphanidermatum on cucumber,Phythium sp. on spinach, Pythium sp. on wheat, Phthium debaryanum ontobacco, Pythium rot (i.e., P. aphanidermatum, P. debaryanum, P.irregulare, P. myriotylum, P. ultimum) on soybean and so forth.

Accordingly, the phosphoramidothionates (I) can be used as activeingredients in fungicidal compositions which can be applied to plowedfields, orchards, tea-field, mulberry-field, meadow, lawn and so on.

The phosphoramidothionates (I) may be produced by the reaction of aphosphoramidochloridothionate of the formula: ##STR3## wherein R₁ and R₂are each as defined above with a 0.9-1.1 mole of a phenol of theformula:

    R.sub.3 OH                                                 (III)

wherein R₃ is as defined above in a solvent in the presence of a 0.9-1.1mole of a hydrogen halide removing agent per 1 mole of thephosphoramidochloridothionate (II) at a temperature of 20° to 120° C.for a period of 1 to 5 hours, or by the reaction of aphosphorochloridothionate of the formula: ##STR4## wherein R₂ and R₃ areeach as defined above with a 1.0-1.2 mole of an amine of the formula:

    R.sub.1 NH.sub.2                                           (V)

wherein R₁ is as defined above in a solvent in the presence of a 1.0-2.2mole of a hydrogen halide removing agent per 1 mole of thephosphorochloridothionate (IV) at a temperature of 0° to 50° C. for aperiod of 1 to 5 hours.

Examples of the solvent are an aromatic hydrocarbon (e.g. benzene,toluene, xylene), a halogenated hydrocarbon (e.g. chloroform, carbontetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), an ether(e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran,diethyleneglycol dimethyl ether), a ketone (e.g. acetone,methylethylketone, cyclohexanone), a nitro compound (e.g. nitroethane,nitrobenzene), a nitrile (e.g. acetonitrile), a tertiary amine (e.g.pyridine, triethylamine, N,N-diethylaniline, tributylamine,N-methylmorpholine), an acid amide (e.g. N,N-dimethylformamide,N,N-dimethylacetamide), water and a mixture thereof.

Examples of the hydrogen halide removing agent are an organic base (e.g.pyridine, triethylamine, N,N-diethylaniline) and an inorganic base (e.g.sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate).

After completion of the reaction, the reaction product may be isolatedby an ordinary separation procedure and, if necessary, purified by aconventional purification procedure such as chromatography, distillationor recrystallization.

Some typical examples of the production of the phosphoramidothionates(I) are shown in the following Examples.

EXAMPLE 1

To a stirred solution of 4,5-methylenedioxy-2-nitrophenol (1.83 g, 10mmol) in acetonitrile (30 ml) was added anhydrous potassium carbonate(1.40 g, 10 mmol). The mixture was kept at 40°-50° C. for 30 minutes.O-Methyl N-1-(methoxymethyl)propyl phosphoramidochloridothionate (2.32g, 10 mmol) was added dropwise thereto and refluxed for 3 hours tocomplete the reaction. Then, the reaction mixture was filtered, and thefiltrate was evaporated under reduced pressure. The residue wasdissolved in toluene (50 ml), and the solution was washed with anaqueous solution of sodium hydroxide, diluted hydrochloric acid andwater and dried over magnesium sulfate. Toluene was evaporated to givean oil which was subjected to chromatography on silica gel to giveO-methyl O-4,5-methylenedioxy-2-nitrophenyl N-1-(methoxymethyl)propylphosphoramidothionate (Compound No. 31) (2.30 g). Yield, 60.8%. n_(D) ²⁵1.5505.

EXAMPLE 2

To a toluene solution (50 ml) containing O-ethylO-4,5-methylenedioxy-2-nitrophenyl phosphorchloridothionate (3.23 g, 10mmol) were added 1-(methoxymethyl)ethylamine (0.89 g, 10 mmol) andtriethylamine (1.1 g, 10 mmol), successively, at 0° C. in 40 minutes.The mixture was stirred at room temperature for an additional 3 hours.After completion of the reaction, the resultant mixture was washed withdiluted hydrochloric acid and water. The solution was dried overmagnesium sulfate, and toluene was evaporated to give O-ethylO-4,5-methylenedioxy-2-nitrophenyl N-1-(methoxymethyl)ethylphosphoramidothionate (Compound No. 22) (4.11 g). Yield, 91.1%. n_(D)²⁷.5 1.5590.

EXAMPLE 3

To a stirred solution of 3,5-dimethoxyphenol (1.54 g, 10 mmol) inacetonitrile (40 ml) was added anhydrous potassium carbonate (1.40 g, 10mmol). The mixture was kept at 40°-50° C. for 30 minutes. O-methylN-isopropyl phosphoramidochloridothionate (1.88 g, 10 mmol) was addeddropwise thereto in 1 hour and the resultant mixture was refluxed for 3hours. After completion of the reaction, the solution was filtered andthe filtrate was evaporated under reduced pressure. The residue wasdissolved in toluene (50 ml). The toluene solution was washed with anaqueous solution of sodium hydroxide, diluted hydrochloric acid andwater and dried over magnesium sulfate. Toluene was evaporated to givean oil which was subjected to column chromatography on silica gel.Evaporation of the solvent gave O-methyl O-3,5-dimethoxyphenylN-isopropyl phosphoramidothionate (Compound No. 66) (1.80 g). Yield,59.1%. n_(D) ¹⁹.5 1.5359.

EXAMPLE 4

To a toluene solution (50 ml) containing O-ethyl O-3,5-dimethoxyphenylphosphorchloridothionate (2.49 g, 10 mmol) were added2-(1-cyano)propylamine (0.84 g, 10 mmol) and triethylamine (1.1 g, 10mmol) successively at 0° C. in 1 hour. The mixture was stirred at roomtemperature for a further 3 hours. After completion of the reaction, theresultant mixture was washed with diluted hydrochloric acid and water.The toluene solution was dried over magnesium sulfate and evaporated togive O-ethyl O-3,5-dimethoxyphenyl N-2-(1-cyano)propylphosphoramidothionate (Compound No. 75) (2.75 g). Yield, 92.9%. n_(D)²⁴.5 1.5368.

EXAMPLE 5

3,4-Methylenedioxyphenol (1.38 g, 10 mmol) and O-ethyl N-isopropylphosphoramidochloridothionate (2.0 g, 10 mmol) were dissolved inacetonitrile (50 ml). Anhydrous potassium carbonate (1.38 g, 10 mmol)was added thereto, and the mixture was refluxed for 4 hours to completethe reaction. Then, the resultant mixture was filtered and the filtratewas evaporated to given an oil, which was dissolved in toluene (50 ml).The solution was washed with an aqueous solution of sodium hydroxide,diluted hydrochloric acid and water, and dried over magnesium sulfate.Evaporation of toluene gave O-ethyl O-3,4-methylenedioxyphenylN-isopropyl phosphoramidothionate (Compound No. 81) (2.21 g). Yield,72.9%. n_(D) ²⁰.0 1.5381.

Examples of the phosphoramidothionate (I) produced in a similar mannerare shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR5##                    (I)                                              Com-                                                                          pound                                 Physical                                No.   R.sub.1      R.sub.2                                                                              R.sub.3     constant                                ______________________________________                                        1    sec-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                       ##STR6##    M.P.46-49°C.                    2    iso-C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                                                       ##STR7##    M.P.85-87°C.                    3    C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                       ##STR8##    M.P.87-90°C.                    4    n-C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.5                                                                       ##STR9##    n.sub.D.sup.25.51.5361                 5    CH.sub.3      C.sub.2 H.sub.5                                                                       ##STR10##   M.P.66-70°C.                    6    n-C.sub.3 H.sub.7                                                                           C.sub.2 H.sub.5                                                                       ##STR11##   n.sub.D.sup.24.51.5572                 7    iso-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                       ##STR12##   n.sub.D.sup.24.51.5532                       ##STR13##    C.sub.2 H.sub.5                                                                       ##STR14##   n.sub.D.sup.24.51.5500                 9    (C.sub.2 H.sub.5).sub.2 CH                                                                  C.sub.2 H.sub.5                                                                       ##STR15##   M.P.84-86°C.                    10   CH.sub.2CHCH.sub.2                                                                          C.sub.2 H.sub.5                                                                       ##STR16##   n.sub.D.sup.24.51.5708                 11   sec-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                              ##STR17##   n.sub.D.sup.24.51.5610                 12   iso-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                              ##STR18##   M.P.90-93°C.                    13   C.sub.2 H.sub.5                                                                             CH.sub.3                                                                              ##STR19##   n.sub.D.sup.24.51.5580                 14   H             C.sub.2 H.sub.5                                                                       ##STR20##   n.sub.D.sup.241.5700                   15   CH.sub.3      CH.sub.3                                                                              ##STR21##   M.P.63-65°C.                    16                                                                                  ##STR22##    C.sub.2 H.sub.5                                                                       ##STR23##   n.sub.D.sup.24.51.5770                 17                                                                                  ##STR24##    C.sub.2 H.sub.5                                                                       ##STR25##   n.sub.D.sup.24.51.5639                 18   HCCCH.sub.2   C.sub.2 H.sub.5                                                                       ##STR26##   n.sub.D.sup.24.51.5809                 19                                                                                  ##STR27##    C.sub.2 H.sub.5                                                                       ##STR28##   M.P.73-75°C.                    20                                                                                  ##STR29##    C.sub.2 H.sub.5                                                                       ##STR30##   M.P.77-79°C.                    21   n-C.sub.3 H.sub.7                                                                           CH.sub.3                                                                              ##STR31##   n.sub.D.sup.24.51.5687                 22                                                                                  ##STR32##    C.sub.2 H.sub.5                                                                       ##STR33##   n.sub.D.sup.27.51.5590                 23                                                                                  ##STR34##    C.sub.2 H.sub.5                                                                       ##STR35##   n.sub.D.sup.27.51.5500                 24   CH.sub.3 OCH.sub.2 CH.sub.2                                                                 C.sub.2 H.sub.5                                                                       ##STR36##   n.sub.D.sup.24.51.5639                 25                                                                                  ##STR37##    C.sub.2 H.sub.5                                                                       ##STR38##   M.P.82-83°C.                    26   CH.sub.3 O(CH.sub.2).sub.3                                                                  C.sub.2 H.sub.5                                                                       ##STR39##   n.sub.D.sup.24.51.5588                 27   C.sub.2 H.sub.5 O(CH.sub.2).sub.2                                                           C.sub.2 H.sub.5                                                                       ##STR40##   n.sub.D.sup.24.51.5556                 28   C.sub.2 H.sub.5 O(CH.sub.2).sub.3                                                           C.sub.2 H.sub.5                                                                       ##STR41##   n.sub.D.sup.24.51.5512                 29                                                                                  ##STR42##    CH.sub.3                                                                              ##STR43##   n.sub.D.sup.21.51.5581                 30                                                                                  ##STR44##    CH.sub.3                                                                              ##STR45##   n.sub.D.sup.21.51.5372                 31                                                                                  ##STR46##    CH.sub.3                                                                              ##STR47##   n.sub.D.sup.251.5505                   32   CH.sub.3 O(CH.sub.2).sub.3                                                                  CH.sub.3                                                                              ##STR48##   M.P.63.5-66°C.                  33   CH.sub.3 O(CH.sub.2).sub.2                                                                  CH.sub.3                                                                              ##STR49##   M.P.76-79°C.                    34   C.sub.2 H.sub.5 O(CH.sub.2).sub.2                                                           CH.sub.3                                                                              ##STR50##   n.sub.D.sup.241.5580                   35   C.sub.2 H.sub.5 O(CH.sub.2).sub.3                                                           CH.sub.3                                                                              ##STR51##   n.sub.D.sup.24.51.5531                 36   (CH.sub.3 O).sub.2 CHCH.sub.2                                                               C.sub.2 H.sub.5                                                                       ##STR52##   n.sub.D.sup.24.5 1.5622                37   (C.sub.2 H.sub.5 O).sub.2 CHCH.sub.2                                                        C.sub.2 H.sub.5                                                                       ##STR53##   n.sub.D.sup.24.51.5350                 38   (CH.sub.3 OCH.sub.2).sub.2 CH                                                               C.sub.2 H.sub.5                                                                       ##STR54##   n.sub.D.sup.251.5445                   39                                                                                  ##STR55##    C.sub.2 H.sub.5                                                                       ##STR56##   n.sub.D.sup.251.5219                   40   NCCH.sub.2 CH.sub.2                                                                         C.sub.2 H.sub.5                                                                       ##STR57##   n.sub.D.sup.24.51.5700                 41   FCH.sub.2 CH.sub.2                                                                          C.sub.2 H.sub.5                                                                       ##STR58##   n.sub.D.sup.24.51.5654                 42   Br(CH.sub.2).sub.3                                                                          C.sub.2 H.sub.5                                                                       ##STR59##   n.sub.D.sup.24.51.5820                 43                                                                                  ##STR60##    C.sub.2 H.sub.5                                                                       ##STR61##   n.sub.D.sup.24.51.5712                 44                                                                                  ##STR62##    C.sub.2 H.sub.5                                                                       ##STR63##   n.sub.D.sup.251.5625                   45                                                                                  ##STR64##    C.sub.2 H.sub.5                                                                       ##STR65##   Resin-ous                              46                                                                                  ##STR66##    CH.sub.3                                                                              ##STR67##   n.sub.D.sup.19.01.5561                 47                                                                                  ##STR68##    C.sub.2 H.sub.5                                                                       ##STR69##   Resin-ous                              48                                                                                  ##STR70##    C.sub.2 H.sub.5                                                                       ##STR71##   n.sub.D.sup.23.01.5702                 49                                                                                  ##STR72##    C.sub.2 H.sub.5                                                                       ##STR73##   M.P.135-140° C.                 50   ClCH.sub.2 CH.sub.2                                                                         C.sub.2 H.sub.5                                                                       ##STR74##   n.sub.D.sup.20.51.5790                 51   BrCH.sub.2 CH.sub.2                                                                         C.sub.2 H.sub.5                                                                       ##STR75##   n.sub.D.sup.21.01.5880                 52                                                                                  ##STR76##    C.sub.2 H.sub.5                                                                       ##STR77##   n.sub.D.sup.21.51.5968                 53                                                                                  ##STR78##    C.sub.2 H.sub.5                                                                       ##STR79##   Resin-ous                              54                                                                                  ##STR80##    C.sub.2 H.sub.5                                                                       ##STR81##   Resin-ous                              55   NCCH.sub.2    C.sub.2 H.sub.5                                                                       ##STR82##   n.sub.D.sup.20.01.5803                 56                                                                                  ##STR83##    C.sub.2 H.sub.5                                                                       ##STR84##   n.sub.D.sup.20.01.5648                 57                                                                                  ##STR85##    CH.sub.3                                                                              ##STR86##   M.P.110-112° C.                 58                                                                                  ##STR87##    CH.sub.3                                                                              ##STR88##   n.sub.D.sup.19.01.5561                 59   HCCCH.sub.2 S(CH.sub.2).sub.2                                                               C.sub. 2 H.sub.5                                                                      ##STR89##   n.sub.D.sup.22.01.5880                 60   CH.sub.3 S(CH.sub.2).sub.2                                                                  C.sub.2 H.sub.5                                                                       ##STR90##   n.sub.D.sup.23.01.5781                 61   CH.sub.3      CH.sub.3                                                                              ##STR91##   n.sub.D.sup.211.5397                   62   C.sub.2 H.sub.5                                                                             CH.sub.3                                                                              ##STR92##   n.sub.D.sup.21.51.5380                 63   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                       ##STR93##   n.sub.D.sup.21.51.5334                 64   n-C.sub.3 H.sub.7                                                                           CH.sub.3                                                                              ##STR94##   n.sub.D.sup.21.51.5284                 65   n-C.sub.3 H.sub.7                                                                           C.sub.2 H.sub. 7                                                                      ##STR95##   n.sub.D.sup.21.51.5320                 66   iso-C.sub.3 H.sub.7                                                                         CH.sub.3                                                                              ##STR96##   n.sub.D.sup.19.51.5359                 67   iso-C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                                                       ##STR97##   n.sub.D.sup.21.01.5269                 68   n-C.sub.4 H.sub.9                                                                           CH.sub.3                                                                              ##STR98##   n.sub.D.sup.201.5291                   69   n-C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.5                                                                       ##STR99##   n.sub.D.sup.201.5244                   70   iso-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                              ##STR100##  n.sub.D.sup.201.5326                   71   iso-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                       ##STR101##  n.sub.D.sup.20 1.5271                  72   sec-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                              ##STR102##  n.sub.D.sup.19.01.5329                 73   sec-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                       ##STR103##  n.sub.D.sup.23.51.5262                 74                                                                                  ##STR104##   C.sub.2 H.sub.5                                                                       ##STR105##  n.sub.D.sup.23.51.5300                 75                                                                                  ##STR106##   C.sub.2 H.sub.5                                                                       ##STR107##  n.sub.D.sup.24.51.5368                 76                                                                                  ##STR108##   C.sub.2 H.sub.5                                                                       ##STR109##  n.sub.D.sup.23.51.5260                 77                                                                                  ##STR110##   CH.sub.3                                                                              ##STR111##  n.sub.D.sup.251.5215                   78   sec-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                       ##STR112##  n.sub.D.sup.21.51.5327                 79                                                                                  ##STR113##   C.sub.2 H.sub.5                                                                       ##STR114##  n.sub.D.sup.25.51.5439                 80   iso-C.sub.3 H.sub.7                                                                         CH.sub.3                                                                              ##STR115##  n.sub.D.sup.20.01.5427                 81   iso-C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                                                       ##STR116##  n.sub.D.sup.20.01.5381                 ______________________________________                                    

In actual application as fungicides, the phosphoramidothionates (I) maybe used alone without incorporation of other ingredients such ascarriers and diluents or, for easier application, in admixture withsolid or liquid carriers. The fungicidal compositions can be formulatedinto any of ordinarily adopted forms such as, for example, dusts,granules, wettable powders, emulsifiable concentrates or flowables.

The fungicidal composition of the invention generally contains 0.1 to99.9% by weight, preferably 2.0 to 80.0% by weight of the activeingredient.

As the solid carriers or diluents usable for formulation of thefungicidal composition, there may be exemplified plant carriers (e.g.wheat flour, tobacco powder, soybean powder, walnut-shell powder, woodenpowder, saw dust, wheat bran, bark dust, cellulose powder, extractresidue), fibrous products (e.g. paper, card board, rag), crushedsynthetic resins, clays (e.g. kaoline, bentonite, terra alba), talcs,other inorganic minerals (e.g. pyrophyllite, celicite, pumice, sulfurpowder, diatomaceous earth, white carbon, activated carbon), chemicalfertilizers (e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, urea, ammonium chloride), etc. As the liquid carriers ordiluents, there may be employed water, alcohols (e.g. methanol,ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g.diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatichydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene),aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters,nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide),halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, carbontetrachloride), etc.

In addition to the solid or liquid carriers or diluents as exemplifiedabove, there may be used surfactants when desired. Examples of thesurfactants are polyoxyethylene phenylphenol polymer, polyoxyethylenealkylaryl ether, sodium laurylsulfate, calcium alkylbenzenesulfonate,alkylsulfates, alkylsulfonates, alkylarylsulfonates, polyethyleneglycolethers, polyvalent alcohol esters, etc. There may be also used adhesiveagents, dispersing agents, stabilizers, etc. Their specific examples arecasein, gelatin, starch, carboxymethyl cellulose, gum arabic, alginate,calcium ligninsulfonate, bentonite, molasse, polyvinyl alcohol, palmoil, agar, isopropyl phosphate, tricresyl phosphate, tall oil,epoxylated oil, surfactants, aliphatic acids and their esters, etc.

Some typical examples of the fungicidal composition according to thisinvention are shown below. In those examples, part(s) and % are byweight unless otherwise indicated.

EXAMPLE A

Compound No. 1 (2 parts), clay (88 parts) and talc (10 parts) werethoroughly pulverized and mixed together to obtain a dust containing 2%of the active ingredient.

EXAMPLE B

Compound No. 25 (50 parts), synthetic silicon oxide hydrate (45 parts),a wetting agent (sodium laurylsulfate) (2 parts) and a dispersing agent(calcium ligninsulfonate) (3 parts) were thoroughly pulverized and mixedtogether to obtain a wettable powder containing 50% of the activeingredient.

EXAMPLE C

Compound No. 22 (10 parts), xylene (70 parts) and polyoxyethylenestyrylphenyl ether (14 parts) and calcium dodecylbenzenesulfonate (6parts) as emulsifiers were mixed together to obtain an emulsifiableconcentrate containing 10% of the active ingredient.

EXAMPLE D

Compound No. 49 (2 parts), synthetic silicon oxide hydrate (1 part), asurfactant (calcium ligninsulfonate) (2 parts), bentonite (30 parts) andclay (65 parts) were mixed together while being powdered. The mixturewas then kneaded with water, granulated and dried to obtain granules.

EXAMPLE E

Compound No. 71 (25 parts), polyoxyethylenesorbitan monooleate (3parts), carboxymethyl cellulose (3 parts) and water (69 parts) weremixed together and pulverized until the particle size of the activeingredient becomes less than 5 microns to obtain flowables.

These compositions comprising the phosphoramidothionates (I) may beapplied as such, or after diluted with water, to the plant in suitableapplication modes such as spraying, perfusion, dusting, etc. Forinstance, they may be applied to the plant for foliar treatment.Further, for instance, they may be spread over, perfused into or admixedwith soil for soil treatment. If necessary, they may be used togetherwith other fungicides to improve their activity as fungicides, and insome cases, a synergistic effect can be expected. They may be alsoapplied in combination with insecticides, acaricides, nematocides,herbicides, plant growth regulators, fertilizers, soil improvers, etc.

A suitable amount of the fungicidal composition of the invention to beapplied is generally from 0.5 to 500 grams, preferably 1 to 200 grams,in terms of the active ingredient per are. In case of the compositionform such as wettable powder, emulsifiable concentrate or flowables, itis normally diluted with water before the application, and theconcentration of the active ingredient is preferably within the range of0.0005 to 0.5% by weight, preferably 0.001 to 0.2% by weight. In case ofthe composition form such as dust or granule, it is ordinarily appliedas such.

The following examples show some typical test results supporting theexcellent fungicidal activity of the phosphoramidothionates (I). Inthese examples, the compound numbers correspond to those in Table 1. Thecompounds used for comparison are as follows:

    ______________________________________                                        Compound                                                                              Structure         Remarks                                             ______________________________________                                                 ##STR117##       Commercially avail- able fungicide "Daconil"        B                                                                                      ##STR118##       Commercially avail- able fungicide "Zineb"          C                                                                                      ##STR119##       Commercially avail- able fungicide "Maneb"          ______________________________________                                    

The fungicidal activities are expressed by the numerals 5, 4, 3, 2, 1and 0, which represent the proportion of infected area on leaf and stemaccording to the following criteria:

    ______________________________________                                        Fungicidal activity                                                                          State of infection                                             ______________________________________                                        5              No infected area                                               4              Infected area of about 10%                                                    in the area of leaf and stem                                   3              Infected area of about 30%                                                    in the area of leaf and stem                                   2              Infected area of about 50%                                                    in the area of leaf and stem                                   1              Infected area of about 70%                                                    in the area of leaf and stem                                   0              Infected area of not less than                                                70% in the area of leaf and stem                               ______________________________________                                    

EXAMPLE I

Seeds of cucumber (species: "Sagamihanjiro") were sowed in soil filledin plastic pots and cultivated in a greenhouse for 14 days to obtainseedlings of cucumber having cotyledons. An aqueous dilution of the testcompound in the form of emulsifiable concentrate was applied onto theseedlings by foliar treatment. Then, a spore suspension ofPseudoperonospora cubensis was sprayed onto the seedlings, which wereplaced at 20° C. under a humid condition for 3 days and grown at 20° C.under the irradiation with a fluorescent lamp for 3 days. The fungicidalactivity was observed, of which the results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Compound   Concentration of                                                                              Fungicidal                                         No.        active ingredient (ppm)                                                                       activity                                           ______________________________________                                         1         500             5                                                   2         500             5                                                   3         500             5                                                   4         500             5                                                   5         500             5                                                   6         500             5                                                   7         500             5                                                   8         500             5                                                   9         500             5                                                  10         500             5                                                  11         500             5                                                  12         500             5                                                  13         500             5                                                  14         500             5                                                  15         500             5                                                  16         500             5                                                  17         500             5                                                  18         500             5                                                  19         500             5                                                  20         500             5                                                  21         500             5                                                  22         500             5                                                  23         500             5                                                  24         500             5                                                  25         500             5                                                  26         500             5                                                  27         500             5                                                  28         500             5                                                  29         500             5                                                  30         500             5                                                  31         500             5                                                  32         500             5                                                  33         500             5                                                  34         500             5                                                  35         500             5                                                  36         500             5                                                  37         500             5                                                  38         500             5                                                  39         500             5                                                  40         500             5                                                  41         500             5                                                  42         500             5                                                  43         500             5                                                  44         500             5                                                  45         500             5                                                  46         500             5                                                  47         500             5                                                  48         500             5                                                  49         500             5                                                  50         500             5                                                  51         500             5                                                  52         500             5                                                  53         500             5                                                  54         500             5                                                  55         500             5                                                  56         500             5                                                  57         500             5                                                  58         500             5                                                  59         500             5                                                  60         500             5                                                  61         500             5                                                  62         500             5                                                  63         500             5                                                  64         500             5                                                  65         500             5                                                  66         500             5                                                  67         500             5                                                  68         500             5                                                  69         500             5                                                  70         500             5                                                  71         500             5                                                  72         500             5                                                  73         500             5                                                  74         500             5                                                  75         500             5                                                  76         500             5                                                  77         500             5                                                  78         500             5                                                  79         500             5                                                  80         500             5                                                  81         500             5                                                  A          500             0                                                  ______________________________________                                    

EXAMPLE II

Seeds of cucumber (species: "Sagamihanjiro") were sowed in soil filledin plastic pots and cultivated in a greenhouse for 14 days to obtainseedlings of cucumber having cotyledons. A spore suspension ofPseudoperonospora cubensis was sprayed onto the seedlings, which wereplaced at 20° C. under a humid condition for 1 day. An aqueous dilutionof the test compound in the form of emulsifiable concentrate was appliedonto the seedlings by foliar treatment. Then, the plants were grown at20° C. under irradiation with a fluorescent lamp for 4 days. Thefungicidal activity was observed, of which the results are shown inTable 3.

                  TABLE 3                                                         ______________________________________                                        Compound   Concentration of                                                                              Fungicidal                                         No.        active ingredient (ppm)                                                                       activity                                           ______________________________________                                         1         200             5                                                   2         200             5                                                   3         200             5                                                   6         200             5                                                   7         200             5                                                   9         200             5                                                  10         200             5                                                  11         200             5                                                  12         200             5                                                  16         200             5                                                  17         200             5                                                  19         200             5                                                  20         200             5                                                  21         200             5                                                  22         200             5                                                  23         200             5                                                  24         200             5                                                  25         200             5                                                  26         200             5                                                  29         200             5                                                  31         200             5                                                  32         200             5                                                  38         200             5                                                  40         200             5                                                  41         200             5                                                  42         200             5                                                  43         200             5                                                  44         200             5                                                  45         200             5                                                  46         200             5                                                  45         200             5                                                  46         200             5                                                  47         200             5                                                  48         200             5                                                  50         200             5                                                  51         200             5                                                  54         200             5                                                  55         200             5                                                  57         200             5                                                  58         200             5                                                  60         200             5                                                  64         200             5                                                  65         200             5                                                  66         200             5                                                  68         200             5                                                  69         200             5                                                  72         200             5                                                  74         200             5                                                  75         200             5                                                  77         200             5                                                  79         200             5                                                  80         200             5                                                  81         200             5                                                  A          200             0                                                  ______________________________________                                    

EXAMPLE III

Seeds of cucumber (species: "Sagamihanjiro") were sowed in soil filledin plastic pots and cultivated in a greenhouse for 14 days to obtainseedlings of cucumber having cotyledons. The seedlings were treated bysoildrench with an aqueous dilution of the test compound in the form ofemulsifiable concentrate. After 6 days, a spore suspension ofPseudoperonospora cubensis was sprayed onto the seedlings, which wereplaced at 20° C. under a humid condition for 1 day and then grown at 20°C. under the irradiation with a fluorescent lamp for 5 days. Thefungicidal activity was observed, of which the results are shown inTable 4.

                  TABLE 4                                                         ______________________________________                                        Compound     Amount of active                                                                           Fungicidal                                          No.          ingredient (g/are)                                                                         activity                                            ______________________________________                                         3           200          5                                                    5           200          5                                                   10           200          5                                                   12           200          5                                                   13           200          5                                                   16           200          5                                                   18           200          5                                                   20           200          5                                                   22           200          5                                                   23           200          5                                                   24           200          5                                                   26           200          5                                                   27           200          5                                                   29           200          5                                                   30           200          5                                                   31           200          5                                                   32           200          5                                                   33           200          5                                                   38           200          5                                                   39           200          5                                                   41           200          5                                                   46           200          5                                                   50           200          5                                                   55           200          5                                                   59           200          5                                                   A            500          0                                                   ______________________________________                                    

EXAMPLE IV

Seeds of grape (species: "Neomus") were sowed in soil filled in plasticpots and cultivated in a greenhouse for 50 days to obtain seedlings ofgrape at the 2 to 3-leaved stage. A spore suspension of Plasmoparaviticola was sprayed onto the seedlings, which were placed at 23° C.under a humid condition for 1 day. Then, an aqueous dilution of the testcompound in the form of emulsifiable concentrate was applied onto theseedlings by foliar treatment. Thereafter, the seedlings were grown at23° C. under the irradiation with a fluorescent lamp for 14 days. Thefungicidal activity was observed, of which the results are shown inTable 5.

                  TABLE 5                                                         ______________________________________                                        Compound   Concentration of                                                                              Fungicidal                                         No.        active ingredient (ppm)                                                                       activity                                           ______________________________________                                         1         500             5                                                   2         500             5                                                   3         500             5                                                   6         500             5                                                   7         500             5                                                   9         500             5                                                  10         500             5                                                  11         500             5                                                  12         500             5                                                  13         500             5                                                  16         500             5                                                  22         500             5                                                  23         500             5                                                  24         500             5                                                  25         500             5                                                  26         500             5                                                  28         500             5                                                  29         500             5                                                  30         500             5                                                  31         500             5                                                  32         500             5                                                  33         500             5                                                  36         500             5                                                  38         500             5                                                  39         500             5                                                  40         500             5                                                  41         500             5                                                  43         500             5                                                  44         500             5                                                  45         500             5                                                  46         500             5                                                  47         500             5                                                  48         500             5                                                  50         500             5                                                  51         500             5                                                  53         500             5                                                  54         500             5                                                  56         500             5                                                  57         500             5                                                  58         500             5                                                  59         500             5                                                  60         500             5                                                  62         500             5                                                  63         500             5                                                  64         500             5                                                  65         500             5                                                  66         500             5                                                  68         500             5                                                  69         500             5                                                  70         500             5                                                  72         500             5                                                  73         500             5                                                  74         500             5                                                  75         500             5                                                  81         500             5                                                  B          1000            0                                                  ______________________________________                                    

EXAMPLE V

Seeds of potato (species: "Danshaku") were sowed in soil filled inplastic pots and cultivated in a greenhouse for 2 months to obtainseedlings of potato. A spore suspension of Phytophthora infestans weresprayed onto the seedlings, which were placed at 20° C. under a humidcondition for 1 day. Then, an aqueous dilution of the test compound inthe form of emulsifiable concentrate was applied onto the seedlings byfoliar treatment. Thereafter, the seedlings were grown at 20° C. under ahumid condition for 6 days. The fungicidal activity was observed, ofwhich the results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Compound   Concentration of                                                                              Fungicidal                                         No.        active ingredient (ppm)                                                                       activity                                           ______________________________________                                         1         500             5                                                   2         500             5                                                   7         500             5                                                  11         500             5                                                  12         500             5                                                  22         500             5                                                  23         500             5                                                  25         500             5                                                  29         500             5                                                  30         500             5                                                  31         500             5                                                  38         500             5                                                  42         500             5                                                  45         500             5                                                  46         500             5                                                  47         500             5                                                  48         500             5                                                  53         500             5                                                  54         500             4                                                  57         500             4                                                  58         500             4                                                  64         500             4                                                  65         500             3                                                  66         500             3                                                  68         500             5                                                  69         500             5                                                  70         500             4                                                  73         500             4                                                  74         500             4                                                  75         500             4                                                  80         500             3                                                  C          1000            0                                                  ______________________________________                                    

What is claimed is:
 1. A phosphoramidothionate of the formula:##STR120## wherein R₁ is a hydrogen atom, a lower alkyl group, a loweralkenyl group, a lower alkynyl group, a lower cycloalkyl group, a lowercycloalkyl(lower)alkyl group, a halo(lower)alkyl group, a loweralkoxy(lower)alkyl group, a di(lower)alkoxy(lower)alkyl group, acyano(lower)alkyl group, a lower alkylthio(lower)alkyl group, a loweralkynylthio(lower)alkyl group, a lower dioxothiacycloalkyl group, alower thiacycloalkyl group, a lower oxacycloalkyl group, a loweroxacycloalkyl(lower)alkyl group or a thienyl(lower)alkyl group and R₂ isa lower alkyl group.
 2. The phosphoramidothionate according to claim 1,wherein R₁ is a hydrogen atom, a C₁ -C₅ alkyl group, a C₃ -C₄ alkenylgroup, a C₃ alkynyl group, a C₃ -C₆ cycloalkyl group, a C₃cycloalkyl(C₂)alkyl group, a halo(C₂ -C₃)alkyl group, a C₁ -C₂ alkoxy(C₂-C₄)alkyl group, a di(C₁ -C₂)alkoxy(C₂)alkyl group, a cyano(C₁ -C₃)alkylgroup, a C₁ alkylthio(C₃)alkyl group, a C₃ alkynylthio(C₂)alkyl group, a1,1-dioxotetrahydrothien-3-yl group, a tetrahydrothiopyran-4-yl group, atetrahydropyran-4-yl group, a tetrahydrofurfuryl group, atetrahydrofuryl group, a tetrahydrothienyl group or a 1-(thienyl)ethylgroup and R₂ is a C₁ -C₂ alkyl group.
 3. The phosphoramidothionateaccording to claim 1, wherein R₁ is a hydrogen atom.
 4. Thephosphoramidothionate according to claim 1, wherein R₁ is a lower alkylgroup.
 5. The phosphoramidothionate according to claim 1, wherein R₁ isa lower cycloalkyl group.
 6. The phosphoramidothionate according toclaim 1, wherein R₁ is represented by the formula: ##STR121##
 7. Thephosphoramidothionate according to claim 2, wherein R₁ is represented bythe formula:

    --CH.sub.2 CH═CH.sub.2.


8. The phosphoramidothionate according to claim 2, wherein R₂ is anethyl group.
 9. The phosphoramidothionate according to claim 2, whereinR₁ is represented by the formula: ##STR122##
 10. Thephosphoramidothionate according to claim 2, wherein R₁ is represented bythe formula:

    --CH.sub.2 C.tbd.CH.


11. The phosphoramidothionate according to claim 2, wherein R₁ isrepresented by the formula: ##STR123##
 12. The phosphoramidothionateaccording to claim 2, wherein R₁ is represented by the formula:##STR124##
 13. The phosphoramidothionate according to claim 2, whereinR₁ is represented by the formula:

    --(CH.sub.2).sub.2 SCH.sub.2 CCH.


14. A phosphoramidothionate of the formula: ##STR125## wherein R₁ is ahydrogen atom, a lower alkyl group, a lower alkenyl group, a loweralkynyl group, a lower cycloalkyl group, a lower cycloalkyl(lower)alkylgroup, a halo(lower)alkyl group, a lower alkoxy(lower)alkyl group, adi(lower)alkoxy(lower)alkyl group, a cyano(lower)alkyl group, a loweralkylthio(lower)alkyl group, a lower alkynylthio(lower)alkyl group, alower dioxothiacycloalkyl group, a lower thiacycloalkyl group, a loweroxacycloalkyl group, a lower oxacycloalkyl(lower)alkyl group or athienyl(lower)alkyl group and R₂ is a lower alkyl group.
 15. Thephosphoramidothionate according to claim 14, whererin R₁ is a hydrogenatom, a C₁ -C₅ alkyl group, a C₃ -C₄ alkenyl group, a C₃ alkynyl group,a C₃ -C₆ cycloalkyl group, a C₃ cycloalkyl(C₂)alkyl group, a halo(C₂-C₃)alkyl group, a C₁ -C₂ alkoxy(C₂ -C₄)alkyl group, a di(C₁-C₂)alkoxy(C₂)alkyl group, a cyano(C₁ -C₃)alkyl group, a C₁alkylthio(C₃)alkyl group, a C₃ alkynylthio(C₂)alkyl group, a1,1-dioxotetrahydrothien-3-yl group, a tetrahydrothiopyran-4-yl group, atetrahydropyran-4-yl group, a tetrahydrofurfuryl group, atetrahydrofuryl group, a tetrahydrothienyl group or a 1-(thienyl)ethylgroup and R₂ is a C₁ -C₂ alkyl group.
 16. The phosphoramidothionateaccording to claim 14, wherein R₁ is a hydrogen atom.
 17. Thephosphoramidothionate according to claim 14, wherein R₁ is a lower alkylgroup.
 18. The phosphoramidothionate according to claim 14, wherein R₁is a lower cycloalkyl group.
 19. The phosphoramidothionate according toclaim 15, wherein R₁ is a propyl group.
 20. The phosphoramidothionateaccording to claim 15, wherein R₂ is either methyl or ethyl.
 21. Afungicidal composition which comprises as an active ingredient afungicidally effective amount of the compound according to claim 8 andan inert carrier or diluent.
 22. A fungicidal composition whichcomprises as an active ingredient a fungicidally effective amount of thecompound according to claim 14 and an inert carrier or diluent.
 23. Amethod for controlling fungi which comprises applying a fungicidallyeffective amount of the phosphoramidothionate according to claim 1 tophytopathogenic fungi.
 24. A method for controlling fungi whichcomprises applying a fungicidally effective amount of thephosphoramidothionate according to claim 14 to phytopathogenic fungi.